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| United States Patent |
5,556,885
|
|
Trotto
, et al.
|
September 17, 1996
|
N-aryl- and N-heteroarylhydrazones of substituted thioacids and the
s-oxides thereof as insecticidal and acaricidal agents
Abstract
There are provided N-arylthiohydrazone derivatives of formula I
##STR1##
the use thereof for the control of insect and acarid pests and methods and
compositions for the protection of crops from the damage and loss caused
by said pests.
| Inventors:
|
Trotto; Susan (Yardley, PA);
Furch, III; Joseph A. (Lawrenceville, NJ);
Kuhn; David G. (Newtown, PA);
Hunt; David A. (Newtown, PA)
|
| Assignee:
|
American Cyanamid Company (Madison, NJ)
|
| Appl. No.:
|
330047 |
| Filed:
|
October 27, 1994 |
| Current U.S. Class: |
514/639; 514/150; 534/567; 534/728; 564/251 |
| Intern'l Class: |
A01N 033/26; C07C 251/80; C07C 245/04; C07C 251/72 |
| Field of Search: |
564/251
534/567,728
514/150,639
|
References Cited
U.S. Patent Documents
| 3332936 | Jul., 1967 | Diekmann | 564/251.
|
| 3423409 | Jan., 1969 | Blatter | 564/251.
|
| 3424723 | Jan., 1969 | Yates et al. | 564/251.
|
| 3829492 | Aug., 1974 | Miller et al. | 564/251.
|
| 3867449 | Feb., 1975 | Moore | 564/251.
|
| 4621156 | Nov., 1986 | Barton et al. | 564/250.
|
| 5246933 | Sep., 1993 | Turnbull et al. | 514/249.
|
| Foreign Patent Documents |
| 2038319 | Jul., 1980 | GB | .
|
Other References
Eistert et al., Chemische Berichte, 1963, vol. 96, No. 9, pp. 2290-2303.
Matsubara et al., Chemical and Pharmaceutical Bulletin, 1985, vol. 33, No.
7, pp. 3009-3011.
Bettarini et al., Pesticide Science, 1994, vol. 40, No. 2, p. 145.
Matsubara et al., Chemical Abstracts, 1988, vol. 108, No. 15, abstract
#131138x. "The Structure and Reactions of (Phenylhydrazonomethylthio)
alkanes" and Nippon Kagaku Kaishi, 1987, No. 7, pp. 1304-1307.
Moon, M. W., Gemrich II, E. G.; Kaugars, G., Journal of Agriculture and
Food Chemistry, 20, (4), 888-91 (1972).
Kaugars, G.; Gemrich, II, E. G.; Rizzo, V. L., Journal of Agriculture and
Food Chemistry, 21, (4), 647-50 (1973).
|
Primary Examiner: Higel; Floyd D.
Attorney, Agent or Firm: Hogan, Jr.; John W.
Claims
What is claimed is:
1. A method for the control of insect or acarid pests which comprises
contacting said pests or their food supply, habitat or breeding grounds
with a pesticidally effective amount of a compound having the structure
##STR29##
wherein A is C-R.sub.3 or N;
B is C-R.sub.4 or N;
W is C-R.sub.5 or N with the proviso that at least one of A, B or W must be
other than N;
Y is halogen, CN, NO.sub.2, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6
haloalkyl, C.sub.1 -C.sub.6 alkoxy or C.sub.1 -C.sub.6 haloalkoxy;
n and m are each independently an integer of 0, 1 or 2;
R is hydrogen; C.sub.1 -C.sub.10 alkyl
unsubstituted or substituted by one or more halogen, C.sub.3 -C.sub.6
cycloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1
-C.sub.4 -alkyl)SO.sub.x, (C.sub.1 -C.sub.4 haloalkyl)SO.sub.x,
phenyl unsubstituted or substituted by one to three halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, (C.sub.1
-C.sub.4 haloalkyl)SO.sub.x, NO.sub.2 or CN groups, or
phenoxy unsubstituted or substituted by one to three halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, (C.sub.1
-C.sub.4 haloalkyl)SO.sub.x, NO.sub.2 or CN groups;
C.sub.3 -C.sub.12 cycloalkyl unsubstituted or substituted by one or more
halogens, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, (C.sub.1 -C.sub.4 haloalkyl)SO.sub.x,
phenyl unsubstituted or substituted by one to three halogen, C.sub.1
-C.sub.4 alkyl C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
phenoxy unsubstituted or substituted by one to three halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups; or
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups with the proviso that
when R is phenyl, then m must be 1 or 2;
R.sub.1 is hydrogen; C.sub.1 -C.sub.10 alkyl unsubstituted or substituted
by one or more halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4
haloalkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2
R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl unsubstituted or substituted by one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl unsubstituted or substituted by one or more halogen,
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4
alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
C.sub.2 -C.sub.10 alkenyl unsubstituted or substituted by one or more
halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl unsubstituted or substituted by one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 halo-alkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
C.sub.2 -C.sub.10 alkynyl unsubstituted or substituted by one or more
halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl one to three halogen, C.sub.1 -C.sub.4 alkyl,
C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4
haloalkoxy, NO.sub.2 or CN groups,
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups; or
C.sub.3 -C.sub.12 cycloalkyl unsubstituted or substituted by one or more
halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl unsubstituted or substituted by one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
R.sub.2 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sub.3, R.sub.4 and R.sub.5 are each independently hydrogen, halogen, CN,
NO.sub.2, (C.sub.1 C-.sub.4 alkyl)SO.sub.x, (C.sub.1 -C.sub.4
haloalkyl)SO.sub.x,
C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 alkoxy
or C.sub.1 -C.sub.6 halo-alkoxy;
R.sub.6, R.sub.7 and R.sub.8 are each independently hydrogen or C.sub.1
-C.sub.4 alkyl;
R.sub.9 is NR.sub.11 R.sub.12,
##STR30##
R.sub.10 is
##STR31##
R.sub.11, R.sub.12, R.sub.13 and R.sub.14 are each independently hydrogen
or C.sub.1 -C.sub.4 alkyl;
X is O, S or NR.sub.13;
r is an integer of 0 or 1;
p and q are each independently an integer of 0, 1, 2, or 3 with the proviso
the sum of p+q+r must be 4, 5 or 6;
x is an integer of 0, 1 or 2; or
the acid addition salts thereof.
2. The method according to claim 1 wherein m is 1 or2.
3. The method according to claim 1 wherein A is CR.sub.3 ; B is C-R.sub.4 ;
W is C-R.sub.5 ; Y is halogen; n is 1 and R.sub.2 is hydrogen.
4. The method according to claim 1 wherein R is C.sub.1 -C.sub.10 alkyl
unsubstituted or substituted by one or more halogen or C.sub.3 -C.sub.6
cycloalkyl unsubstituted or substituted by one or more halogen or C.sub.1
-C.sub.4 alkyl groups and R.sub.1 is C.sub.1 -C.sub.10 alkyl unsubstituted
or substituted by one or more halogen atoms or phenyl groups, C.sub.2
-C.sub.10 alkenyl unsubstituted or substituted by one or more halogen
atoms or phenyl unsubstituted or substituted by one or more halogen atoms.
5. The method according to claim 2 wherein R, R.sub.1 and R.sub.2 are each
independently Hydrogen or C.sub.1 -C.sub.10 alkyl.
6. The method according to claim 2 wherein A is C-R.sub.3 ; B is C-R.sub.4
; W is C-R.sub.5 ; Y is halogen; n is 1; R.sub.2 is hydrogen and R.sub.3,
R.sub.4, and R.sub.5 are each independently hydrogen, halogen or C.sub.1
-C.sub.6 haloalkyl.
7. The method according to claim 6 wherein m is 2.
8. The method according to claim 6 wherein the compound is
S-ethyl-2,2-dimethylthiopriopionate,
2-(2,6-dichloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)hydrazone; the
S-oxide thereof; the S,S-dioxide thereof or their acid addition salts.
9. A method for the protection of growing plants from attack or infestation
by insect or acarid pests which comprises applying to the foliage of the
plants, or to the soil or water in which they are growing, a pesticidally
effective amount of a compound having the structure
##STR32##
wherein A, B, W, Y, n, R, R.sub.1, R.sub.2, and m are described in claim
1.
10. The method according to claim 9 wherein m is 1 or 2.
11. The method according to claim 9 wherein A is C-R.sub.3 ; B is C-R.sub.4
; W is C-R.sub.5 ; Y is halogen; n is 1 and R.sub.2 is hydrogen.
12. The method according to claim 10 wherein A is C-R.sub.3 ; B is
C-R.sub.4 ; W is C-R.sub.5 ; Y is halogen, n is 1; R.sub.2 is hydrogen;
R.sub.3, R.sub.4 and R.sub.5 are each independently hydrogen, halogen or
C.sub.1 -C.sub.6 haloalkyl; R.sub.is C.sub.1 -C.sub.10 alkyl unsubstituted
or substituted by one or more halogen atoms or C.sub.3 -C.sub.6 cycloalkyl
unsubstituted or substituted by one or more halogen or C.sub.1 -C.sub.4
alkyl groups and R.sub.1 is C.sub.1 -C.sub.10 alkyl unsubstituted or
substituted by one or more halogen or phenyl groups, C.sub.2 -C.sub.10
alkenyl unsubstituted or substituted by one or more halogen atoms or
phenyl unsubstituted or substituted by one or more halogen atoms.
13. The method according to claim 11 wherein the compound is
S-ethyl-2,2-dimethylthiopropionate,
2-(2,6-dichloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)hydrazone; the
S-oxide thereof; the S,S-dioxide thereof or their acid addition salts.
14. A compound having the structure of formula I
##STR33##
wherein A is C-R.sub.3 or N;
B is C-R.sub.4 or N;
W is C-R.sub.5 or N with the proviso that at least one of A, B or W must be
other than N;
Y is halogen, CN, NO.sub.2, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6
haloalkyl, C.sub.1 -C.sub.6 alkoxy or C.sub.1 -C.sub.6 haloalkoxy;
n and m are each independently an integer of 0, 1 or 2;
R is C.sub.1 -C.sub.10 alkyl unsubstituted or substituted by one or more
halogen, C.sub.3 -C.sub.6 cycloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4 -alkyl)SO.sub.x, (C.sub.1 -C.sub.4
haloalkyl)SO.sub.x,
phenyl unsubstituted or substituted by one to three halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, (C.sub.1
-C.sub.4 haloalkyl)SO.sub.x, NO.sub.2 or CN groups, or
phenoxy unsubstituted or substituted by one to three halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, (C.sub.1
-C.sub.4 haloalkyl)SO.sub.x, NO.sub.2 or CN groups;
C.sub.3 -C.sub.12 cycloalkyl unsubstituted or substituted by one or more
halogens, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, (C.sub.1 -C.sub.4 haloalkyl)SO.sub.x,
phenyl unsubstituted or substituted by one to three halogen, C.sub.1
-C.sub.4 alkyl C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
phenoxy unsubstituted or substituted by one to three halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups; or
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups with the proviso that
when R is phenyl, then m must be 1 or 2;
R.sub.1 is hydrogen; C.sub.1 -C.sub.10 alkyl unsubstituted or substituted
by one or more halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4
haloalkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, CONR.sub.6 R.sub.7, R.sub.9,
R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl unsubstituted or substituted by one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
C.sub.2 -C.sub.10 alkenyl unsubstituted or substituted by one or more
halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl unsubstituted or substituted by one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 halo-alkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
C.sub.2 -C.sub.10 alkynyl unsubstituted or substituted by one or more
halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl one to three halogen, C.sub.1 -C.sub.4 alkyl,
C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4
haloalkoxy, NO.sub.2 or CN groups,
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups; or
C.sub.3 -C.sub.12 cycloalkyl unsubstituted or substituted by one or more
halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl unsubstituted or substituted by one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl unsubstituted or substituted by one or more halogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
R.sub.2 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sub.3, R.sub.4 and R.sub.5 are each independently hydrogen, halogen, CN,
NO.sub.2, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, (C.sub.1 -C.sub.4
haloalkyl)SO.sub.x,
C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 alkoxy
or C.sub.1 -C.sub.6 halo-alkoxy;
R.sub.6, R.sub.7 and R.sub.8 are each independently hydrogen or C.sub.1
-C.sub.4 alkyl;
R.sub.9 is NR.sub.11 R.sub.12,
##STR34##
R.sub.10 is
##STR35##
R.sub.11, R.sub.12, R.sub.13 and R.sub.14 are each independently hydrogen
or C.sub.1 -C.sub.4 alkyl;
X is O, S or NR.sub.13 ;
r is an integer of 0 or 1;
p and q are each independently an integer of 0, 1, 2, or 3 with the proviso
the sum of p+q+r must be 4, 5 or 6;
x is an integer of 0, 1 or 2; or
the acid addition salts thereof.
15. The compound according to claim 14 having the structure
##STR36##
wherein R is C.sub.1 -C.sub.10 alkyl unsubstituted or substituted by one
or more halogen atoms or
C.sub.3 -C.sub.6 cycloalkyl unsubstituted or substituted by one or more
halogen or C.sub.1 -C.sub.4 alkyl groups; and
R.sub.1 is C.sub.1 -C.sub.10 alkyl unsubstituted or substituted by one or
more halogen or phenyl groups,
C.sub.2 -C.sub.10 alkenyl unsubstituted or substituted by one or more
halogen atoms or
phenyl unsubstituted or substituted by one or more halogen atoms.
16. The compound according to claim 14 wherein m is 1 or 2.
17. The compound according to claim 15 wherein m is 1 or 2.
18. The compound according to claim 15 S-ethyl-2,2-dimethylthiopropionate,
2-(2,6-dichloro-.alpha.,.alpha.,.alpha.-trifluoro-p -tolyl(hydrazone; the
S-oxide thereof; the S,S-dioxide thereof or their acid addition salts.
19. A composition for controlling insect or acarid pests which comprises an
inert liquid or solid carrier and a pesticidally effective amount of a
compound having a structure
##STR37##
wherein A, B, W, Y, n, R, R.sub.1, R.sub.2, and m are described in claim
14.
20. A process for the preparation of a compound of formula Ia
##STR38##
wherein A, B, W, Y, n, R, R.sub.1, and R.sub.2 are described in claim 14
which comprises reacting a compound of formula II
##STR39##
wherein X.sup.1 is halogen with at least one molar equivalent of a
mercaptan of formula III
HS-R.sub.1 (III)
in the presence of a base in the presence or absence of a solvent.
Description
BACKGROUND OF THE INVENTION
Significant global economic losses in major agronomic crop production are
caused by the damage and infestation of insect and acarid pests. Crop
reduction due to said pests, for example in cotton and peanuts, can range
as high as 39% and 78%, respectively. Pest infestation can result in lower
yields, lower crop quality, reduced consumption, increased perishability,
increased risk of disease, higher processing cost, higher transportation
cost and increased market prices. Therefore, new and effective insect and
acarid control agents and crop protection methods are a continuing global
need.
It is an object of this invention to provide N-arylthiohydrazone
derivatives which are effective agents for the control of pestiferous
insects and acarina.
It is another object of this invention to provide a method for the
protection of growing and harvested crops from the harmful and deleterious
effects caused by insect and acarid pests.
It is a further object of this invention to provide insecticidal and
acaricidal compositions.
SUMMARY OF THE INVENTION
The present invention provides N-arylthiohydrazone compounds of formula I
##STR2##
wherein A is C-R.sub.3 or N;
B is C-R.sub.4 or N;
W is C-R.sub.5 or N with the proviso that at least one of A, B or W must be
other than N;
Y is halogen, CN, NO.sub.2, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6
haloalkyl, C.sub.1 -C.sub.6 alkoxy or C.sub.1 -C.sub.6 haloalkoxy;
n and m are each independently an integer of 0, 1 or 2;
R is hydrogen;
C.sub.1 -C.sub.10 alkyl optionally substituted with one or more halogen,
C.sub.3 -C.sub.6 cycloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4
haloalkoxy, (C.sub.1 -C.sub.4 -alkyl) SO.sub.x, (C.sub.1 -C.sub.4
haloalkyl) SO.sub.x, phenyl optionally substituted with one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4 alkyl)
SO.sub.x, (C.sub.1 -C.sub.4 haloalkyl) SO.sub.x, NO.sub.2 or CN groups, or
phenoxy optionally substituted with one to three halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, (C.sub.1 -C.sub.4
haloalkyl)SO.sub.x, NO.sub.2 or CN groups;
C.sub.3 -C.sub.12 cycloalkyl optionally substituted with one or more
halogens, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, (C.sub.1 - C.sub.4 haloalkyl) SO.sub.x,
phenyl optionally substituted with one to three halogen, C.sub.1 -C.sub.4
alkyl C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
phenoxy optionally substituted with one to three halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups; or
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups with the proviso that when R is
phenyl, then m must be an integer of 1 or 2;
R.sub.1 is hydrogen; C.sub.1 -C.sub.10 alkyl optionally substituted with
one or more halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4
haloalkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2
R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
C.sub.2 -C.sub.10 alkenyl optionally substituted with one or more halogen,
hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x,
CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
C.sub.2 -C.sub.10 alkynyl optionally substituted with one or more halogen,
hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x,
CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups; or
C.sub.3 -C.sub.12 cycloalkyl optionally substituted with one or more
halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
R.sub.2 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sub.3, R.sub.4 and R.sub.5 are each independently hydrogen, halogen, CN,
NO.sub.2, (C.sub.1 -C.sub.4 alkyl) SO.sub.x, (C.sub.1 -C.sub.4 haloalkyl)
SO.sub.x, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1
-C.sub.6 alkoxy, or C.sub.1 -C.sub.6 -haloalkoxy;
R.sub.6, R.sub.7 and R.sub.8 are each independently hydrogen or C.sub.1
-C.sub.4 alkyl;
R.sub.9 is NR.sub.11 R.sub.12,
##STR3##
R.sub.10 is
##STR4##
R.sub.11, R.sub.12, R.sub.13 and R.sub.14 are each independently hydrogen
or C.sub.1 -C.sub.4 alkyl;
X is O, S or NR.sub.13 ;
r is an integer of 0 or 1;
p and q are each independently an integer of 0, 1, 2, or 3 with the proviso
that only one of p, q, or r can be 0 and with the further proviso that the
sum of p+q+r must be 4, 5 or 6;
x is an integer of 0, 1 or 2; or the acid addition salts thereof.
Also provided are methods and compositions for the control of insect and
acarid pests and the protection of growing and harvested crops from attack
and infestation thereby.
DETAILED DESCRIPTION OF THE INVENTION
A wide variety of insects and acarina cause great economic loss by damaging
or destroying agricultural crops and horticultural and pharmaceutical
plants; by aiding in the spread and development of bacteria, fungi and
viruses that produce diseases of plants; and by destroying or lowering the
value of stored foods, other products and possessions. Insect and acarid
attack and infestation cause some of the farmers' greatest problems the
world over. The need for alternative and effective insect and acarid
control is a global concern.
It has now been found that the N-arylthiohydrazone compounds of formula I
are highly effective agents for the control of a wide variety of insect
and acarid pests.
The formula I thiohydrazone compounds of the present invention have the
structural formula
##STR5##
wherein A is C-R.sub.3 or N;
B is C-R.sub.4 or N;
W is C-R.sub.5 or N with the proviso that at least one of A, B or W must be
other than N;
Y is halogen, CN, NO.sub.2, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6
haloalkyl, C.sub.1 -C.sub.6 alkoxy or C.sub.1 -C.sub.6 haloalkoxy;
n and m are each independently an integer of 0, 1 or 2;
R is hydrogen;
C.sub.1 -C.sub.10 alkyl optionally substituted with one or more halogen,
C.sub.3 -C.sub.6 cycloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4
haloalkoxy, (C.sub.1 -C.sub.4 -alkyl)SO.sub.x, (C.sub.1 -C.sub.4
haloalkyl)SO.sub.x,
phenyl optionally substituted with one to three halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 - C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4 alkyl) SO.sub.x, (C.sub.1 -C.sub.4
haloalkyl)SO.sub.x, NO.sub.2 or CN groups, or
phenoxy optionally substituted with one to three halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4 alkyl) SO.sub.x, (C.sub.1 -C.sub.4
haloalkyl)SO.sub.x, NO.sub.2 or CN groups;
C.sub.3 -C.sub.12 cycloalkyl optionally substituted with one or more
halogens, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, (C.sub.1 - C.sub.4 haloalkyl)SO.sub.x,
phenyl optionally substituted with one to three halogen, C.sub.1 -C.sub.4
alkyl C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
phenoxy optionally substituted with one to three halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups; or
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups with the proviso that when R is
phenyl, then m must be 1 or 2;
R.sub.1 is hydrogen; C.sub.1 -C.sub.10 alkyl optionally substituted with
one or more halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4
haloalkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2
R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
C.sub.2 -C.sub.10 alkenyl optionally substituted with one or more halogen,
hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x,
CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
C.sub.2 -C.sub.10 alkynyl optionally substituted with one or more halogen,
hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4 alkyl)SO.sub.x,
CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups; or
C.sub.3 -C.sub.12 cycloalkyl optionally substituted with one or more
halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, (C.sub.1 -C.sub.4
alkyl)SO.sub.x, CONR.sub.6 R.sub.7, CO.sub.2 R.sub.8, R.sub.9, R.sub.10,
C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one to three
halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 halalkyl, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, NO.sub.2 or CN groups,
phenyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups, or
pyridyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, NO.sub.2 or CN groups;
R.sub.2 is hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sub.3, R.sub.4 and R.sub.5 are each independently hydrogen, halogen, CN,
NO.sub.2, (C.sub.1 -C.sub.4 alkyl)SO.sub.x, (C.sub.1 -C.sub.4
haloalkyl)SO.sub.x, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl,
C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 haloalkoxy;
R.sub.6, R.sub.7 and R.sub.8 are each independently hydrogen or C.sub.1
-C.sub.4 alkyl;
R.sub.9 is NR.sub.11 R.sub.12,
##STR6##
R.sub.10 is
##STR7##
R.sub.11, R.sub.12, R.sub.13 and R.sub.14 are each independently hydrogen
or C.sub.1 -C.sub.4 alkyl;
X is O, S or NR.sub.13 ;
r is an integer of 0 or 1;
p and q are each independently an integer of 0, 1, 2, or 3 with the proviso
that only one of p, q, or r can be 0 and with the further proviso that the
sum of p+q+r must be 4, 5 or 6;
x is an integer of 0, 1 or 2; and
the acid addition salts thereof.
The term halogen as used in the specification and claims designates
chlorine, fluorine, bromine or iodine. The term haloalkyl designates an
alkyl group, C.sub.n H.sub.2n+1 which contains from one halogen atom to
2n+1 halogen atoms. Similarly, the term haloalkoxy designates a OC.sub.n
H.sub.2n+1 group which contains from one to 2n+1 halogen atoms. The
halogen atoms may be the same or different. The term acid addition salts
designates those salts formed by acids commonly known in the art such as
hydrogen chloride, hydrogen bromide, hydrogen bisulfate, hemi-hydrogen
sulfate and the like. In the above definition of formula I, when n is an
integer of 0 then Y is hydrogen.
Preferred compounds of the invention are those wherein m is 1 or 2; A is
C-R.sub.3 ; B is CR.sub.4 ; W is C-R.sub.5 ; Y is halogen and n is 1. More
preferred compounds are those wherein m is 1 or 2; R is C.sub.1 -C.sub.10
alkyl optionally substituted with one or more halogen atoms or C.sub.3
-C.sub.6 cycloalkyl optionally substituted with one or more halogen or
C.sub.1 -C.sub.4 alkyl groups; R.sub.1 is C.sub.1 -C.sub.6 alkyl
optionally substituted with one or more halogen or phenyl groups; R.sub.3,
R.sub.4 and R.sub.5 are each independently hydrogen, halogen, NO.sub.2 or
C.sub.1 -C.sub.4 haloalkyl; Y is halogen and n is 1.
Those compounds of formula I wherein m is 1 or 2 may be prepared by the
oxidation of the appropriate N-arylthiohydrazone precursor using standard
oxidizing reagents such as m-chloroperbenzoic acid (mcpba), hydrogen
peroxide and acetic acid, KMnO.sub.4 and the like. The reaction is shown
in flow diagram I.
##STR8##
Those compounds of formula I wherein m is 0 may be prepared by reacting the
appropriate hydrazinoyl halide of formula II with a suitable mercaptan of
formula III in the presence of a base as shown in flow diagram II wherein
X.sup.1 is halogen.
##STR9##
Alternatively, the appropriate N-arylthiohydrazide of formula IV may be
reacted with a suitable alkyl or aryl halide of formla V in the presence
of a base to give the desired N-arylthiohydrazone compound of formula Ia.
The reaction is illustrated flow diagram III.
##STR10##
Compounds of formula IV may be readily prepared by those methods known in
the art such as that described in U.S. Pat. No. 5,246,933. Compounds of
formula Ia may be converted to their S-oxide and S,S-dioxide derivatives
as shown hereinabove in flow diagram I.
Growing or harvested crops may be protected from attack or infestation by
insect or acarid pests by applying to the foliage of the crops, or to the
soil or water in which they are growing, a pesticidally effective amount
of a formula I N-arylthiohydrazone derivative.
In actual agronomic practice, generally about 10 ppm to 10,000 ppm,
preferably about 100 to 5,000 ppm of the formula I compound dispersed in a
liquid carrier, when applied to the plants or the soil or water in which
they are growing, is effective to protect the plants from insect and
acarina attack and infestation. Applications, such as spray applications,
of compositions of the invention are generally effective at rates which
provide about 0.125 kg/ha to about 250 kg/ha, preferably about 10 kg/ha to
100 kg/ha of active ingredient. Of course, it is contemplated that higher
or lower rates of application of the N-arylthiohydrazone derivatives may
be used dependent upon the prevailing environmental circumstances such as
population density, degree of infestation, stage of plant growth, soil
conditions, weather conditions and the like.
Advantageously, the formula I compounds may be used in conjunction with, or
in combination with, other biological and chemical control agents
including other insecticides, nematicides, acaricides, molluscicides,
fungicides and bactericides such as nuclear polyhedrosis viruses,
pyrroles, arylpyrroles, halobenzoylureas, pyrethroids, carbamates,
phosphates, and the like.
Typical formulations suitable for the formula I N-arylthiohydrazone
derivatives are granular compositions, flowable compositions, wettable
powders, dusts, microemulsions, emulsifiable concentrates and the like.
All compositions which lend themselves to soil, water and foliage
application and provide effective plant protection are suitable.
Compositions of the invention include the formula I N-arylthiohydrazone
derivative admixed with an inert solid or liquid carrier.
Where compositions of the invention are to be employed in combination
treatments with other biological or chemical agents, the composition may
be applied as an admixture of the components or may be applied
sequentially. While not required, the combination composition comprising a
formula I compound and a co-pesticide may also comprise other components,
for example, fertilizers, inert formulation aides such as surfactants,
emulsifiers, defoamers, dyes, extenders and the like.
In order to aid in the understanding of the invention, specific examples
thereof are set forth below. The invention described and claimed herein is
not to be limited in scope by these merely illustrative examples. Indeed,
various modifications of the invention in addition to those exemplified
and described herein will become apparent to those skilled in the art from
the following examples and the foreging description. Such modifications
are also intended to fall within the scope of the appended claims. The
terms .sup.1 H, .sup.13 C, .sup.19 FNMR designate proton, carbon and
fluorine nuclear magnetic resonance spectroscopy, respectively. IR
designates infrared spectroscopy and HPLC designates high performance
liquid chromatography.
EXAMPLE 1
Preparation of S-Ethyl-2,2-dimethylthiopropionate, 2-(2,6
dichloro-.alpha.,.alpha.,.alpha.,trifluoro-p-tolyl)hydrazone
##STR11##
A stirred mixture of ethyl mercaptan (1.6 g, 0.0257 mole) and triethylamine
(TEA) (2.87 g, 0.0283 mole) in tetrahydrofuran is treated with a solution
of 1-chloro-2,2-dimethylpropionaldehyde,
2-(2,6-dichloro-.alpha.,.alpha.,.alpha.-trifluoro p-tolyl)hydrazone (8.95
g, 0.0257 mole) in tetrahydrofuran at 25.degree. C. When the reaction is
complete by thin layer chromatographic analysis, the reaction mixture is
poured into water and extracted with ethyl acetate. The combined extracts
are dried over sodium sulfate and concentrated in vacuo to give the title
product as an orange oil, 8.4 g (87.6% yield), identified by IR, .sup.1
HNMR, .sup.13 CNMR, .sup.19 FNMR, mass spectral and C, H, N, S, Cl
elemental analyses.
EXAMPLE 2
Preparation of S-Methyl-2,2-dimethylthiopropionate,
2-(2,4,6-trichlorophenyl)hydrazone
##STR12##
A suspension of 2,2-dimethylthiopropionic acid,
2-(2,4,6-trichlorophenyl)hydrazide (1.37 g, 4.4 mmole) and K.sub.2
CO.sub.3 (0.66 g, 4.8 mmole) is treated dropwise with a solution of methyl
iodide (0.684 g, 4.8 mmole) in acetone at reflux temperature, heated at
reflux temperature for 2 hours, stirred at room temperature for 18 hours
and filtered. The filtrate is concentrated in vacuo to give a brown gum
residue. The residue is taken up in ethyl ether, filtered and this
filtrate is evaporated to dryness in vacuo to give the title product as a
clear red-brown oil, 1.4 g (97.9% yield), identified by IR, .sup.1 HNMR,
mass spectral and C, H, N, S, Cl elemental analyses.
EXAMPLES 3-27
Preparation of N-Arylthiohydrazone Compounds
Using essentially the same procedure described in Examples 1 and 2 and
substituting the appropriate reagents, the following compounds shown in
Table I are prepared. The compounds obtained are oils, except where
indicated, and are identified by .sup.1 HNMR, .sup.13 CNMR, IR, mass
spectral and elemental analyses.
TABLE I
__________________________________________________________________________
##STR13##
Ex. No.
A B W Yn R R.sub.1 % Yield
__________________________________________________________________________
3 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
C.sub.6 H.sub.4 pCl
86.2
4 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 C.sub.6 H.sub.5
69.5
5 CCl CH CCF.sub.3
6-Cl
##STR14##
CH.sub.2 CH.sub.3
74.1
6 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
##STR15## 86.5
7 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
66.7
8 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 CH.sub.2 CH.sub.3
82.2
9 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 (CH.sub.2).sub.2 CH.sub.3
65.8
10* CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
##STR16## 49.2
11 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
C(CH.sub.3).sub.3
76.3
12 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 C.sub.6 H.sub.4 -
87.0
13 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 SC(CH.sub.3).sub.3
88.4
14 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 COOH.sub.3
85.7
15 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH(CH.sub.3).sub.2
80.6
16 CCl CH CCF.sub.3
6-Cl
##STR17##
CH.sub.2 CH.sub.3
85.5
17 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 CF.sub.3
71.1
18 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.3 56.5
19 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 CHCH.sub.2
--
20 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
##STR18## 82.4
21 CCl CH CCl 6-Cl
C(CH.sub.3).sub.3
CH.sub.2 CH.sub.2 CFCF.sub.2
90.5
22 CCl CH CCF.sub.3
6-Cl
##STR19##
CH.sub.3 79.3
23 CCl CH CCF.sub.3
6-Cl
##STR20##
CH.sub.3 83.1
24 CCl CH CCF.sub.3
6-Cl
CH(CH.sub.3).sub.2
CH.sub.3 82.9
25 CCl CH CCF.sub.3
6-Cl
CF.sub.2 CF.sub.3
CH.sub.2 CH.sub.3
5.0
26 CCl CH CCF.sub.3
6-Cl
CF.sub.3 CH.sub.2 CH.sub.3
76.0
27 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2
78.2
__________________________________________________________________________
*mp 81.degree.-84.degree. C.
EXAMPLE 28
Preparation of S-Ethyl-2,2-dimethylthiopropionate,
2-(2,6-dichloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)hydrazone,
S-oxide
##STR21##
A solution of S-ethyl-2,2-dimethylthiopropionate,
2-(2,6-dichloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl) hydrazone (3.73
g, 0.01 mole) in chloroform is treated incrementally with
m-chloroperbenzoic acid (mcpba) (2.88 g of 60 % pure, 0.01 mole) at
-10.degree. to -20.degree. C., maintained at -10.degree. C. for 1 hour,
warmed to room temperature and filtered. The filtrate is concentrated in
vacuo to give a solid residue. Flash column chromatography of the residue
using silica-gel; hexanes, followed by 95: 5 hexanes: ethyl acetate as
eluent, gives the title product as a straw-yellow oil, in 77.1% yield,
identified by IR, .sup.1 HNMR, .sup.13 FNMR, mass spectral and C, H, N,
Cl, F, S elemental analyses.
EXAMPLES 29-33
Preparation of N-Arylthiohydrazone, S-oxide Compounds
Using essentially the same procedure described in Example 28 and
substituting the appropriate N-arylthiohydrazone substrate, the following
compounds shown in Table II are prepared. The compounds obtained are oils,
except where indicated, and are identified by .sup.1 HNMR, .sup.13 CNMR,
IR, mass spectral and elemental analyses.
TABLE II
__________________________________________________________________________
##STR22##
Ex. No.
A B W Yn R R.sub.1
% Yield
__________________________________________________________________________
29* CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.3
58.1
30 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH(CH.sub.3).sub.2
72.1
31* CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 CF.sub.3
22.7
32* CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
cyclohexyl
58.1
33* CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 C.sub.6 H.sub.5
66.7
__________________________________________________________________________
*Soft Solid
**mp 91.degree.-94.degree.-
EXAMPLE 34
Preparation of S-Ethyl-2,2-dimethylthiopropionate,
2-(2,6-dichloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)hydrazone,
S,S-dioxide
##STR23##
A solution of S-Ethyl-2,2-dimethylthiopropionate,
2-(2,6-dichloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)hydrazone (3.73
g, 0.01 mole) and m-chloroperbenzoic acid (mcpba) (6.3 g of 60% pure,
0.022 mole) in tetrahydrofuran is stirred at 25.degree. C. for 3 hours,
(reaction is complete by thin layer chromatographic analysis) and poured
onto water. The resultant mixture is extracted with ethyl ether. The
extracts are combined, washed sequentially with saturated NaHCO.sub.3 and
water and concentrated in vacuo to give a residue. Flash column
chromatography using silica-gel; hexanes gives the title product as a
cream-colored solid, in 67.3% yield, mp 98.degree.-101.degree. C.,
identified by IR, .sup.1 HNMR, .sup.13 CNMR, .sup.19 FNMR and C, H and N
elemental analyses.
EXAMPLES 35-49
Preparation of N-Arylthiohydrazone, S,S-dioxide Compounds
Using essentially the same procedure described in Example 34 and
substituting the appropriate N-arylthiohydrazone substrate, the following
compounds shown in Table III are prepared. All compounds obtained are
identified by .sup.1 HNMR, .sup.13 CNMR, IR, mass spectral and elemental
analyses.
TABLE III
__________________________________________________________________________
##STR24##
Ex. No.
A B W Yn R R.sub.1 mp .degree.C.
% Yield
__________________________________________________________________________
35 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.3 119.5-121.5
29.4
36 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH(CH.sub.3).sub.2
oil 89.4
37 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
cyclohexyl soft solid
78.6
38 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 C.sub.6 H.sub.5
soft solid
94.3
39 CCl CH CCF.sub.3
6-Cl
CF.sub.3 CH.sub.2 CH.sub.3
88.5-90
79
40 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
##STR25## soft solid
58.8
41 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
CH.sub.2 CHCH.sub.2
oil 48.2
42 CCl CH CCl 6-Cl
C(CH.sub.3).sub.3
CH.sub.3 soft solid
94.4
43 CCl CH CCl 6-Cl
C(CH.sub.3).sub.3
CH.sub.2 CH.sub.2 CFCF.sub.2
soft solid
23.0
44 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
C.sub.6 H.sub.4 - pCl
89-91 30.0
45 CCl CH CCF.sub.3
6-Cl
C(CH.sub.3).sub.3
C(CH.sub.3).sub.3
soft solid
66.8
46 CCl CH CCF.sub.3
6-Cl
##STR26##
CH.sub.2 CH.sub.3
70-74 91.4
47 CCl CH CCF.sub.3
6-Cl
##STR27##
CH.sub.3 -- 88.7
48 CCl CH CCF.sub.3
6-Cl
##STR28##
CH.sub.3 oil 35.7
49 CCl CH CCF.sub.3
6-Cl
CH(CH.sub.3).sub.2
CH.sub.3 -- --
__________________________________________________________________________
EXAMPLE 50
Insecticidal Evaluation of N-Arylthiohydrazone Compounds
Test solutions are prepared by dissolving the test compound in a 35%
acetone in water mixture to give a concentration of 10,000 ppm. Subsequent
dilutions are made with water as needed.
Spodoptera eridania, 3rd instar larvae, southern armyworm (SAW)
A Sieva limabean leaf expanded to 7-8 cm in length is dipped in the test
solution with agitation for 3 seconds and allowed to dry in a hood. The
leaf is then placed in a 100.times.10 mm petri dish containing a damp
filterpaper on the bottom and ten 3rd instar caterpillars. At 5 days,
observations are made of mortality, reduced feeding, or any interference
with normal molting.
Diabrotic virgifera vergifera Leconte, 3rd instar western corn rootworm
(WCR)
One cc of fine talc is placed in a 30 ml wide-mouth screw-top glass jar.
One mL of the appropriate acetone test solution is pipetted onto the talc
so as to provide 1.25 mg of active ingredient per jar. The jars are set
under a gentle air flow until the acetone is evaporated. The dried talc is
loosened, 1 cc of millet seed is added to serve as food for the insects
and 25 mL of moist soil is added to each jar. The jar is capped and the
contents thoroughly mixed on a Vortex Mixer. Following this, ten 3rd
instar rootworms are added to each jar and the jars are loosely capped to
allow air exchange for the larvae. The treatments are held for 5 days when
mortality counts are made. Missing larvae are presumed dead, since they
decompose rapidly and can not be found. The concentrations used in this
test correspond approximately to 50 kg/ha.
Heliothis virenscens, 3rd instar tobacco budworm (TBW)
Cotton cotyledons are dipped in the test solution and allowed to dry in a
hood. When dry, each is cut into quarters and ten sections are placed
individually in 30 mL plastic medicine cups containing a 5 to 7 mm long
piece of damp dental wick. One 3rd instar caterpillar is added to each cup
and a cardboard lid placed on the cup. Treatments are maintained for 3
days before mortality counts and estimates of reduction in feeding damage
are made.
The tests are rated according to the scale shown below and the data
obtained are shown in Table IV. When more than one test is conducted, the
results are averaged.
______________________________________
RATING SCALE
Rate % Mortality Rate % Mortality
______________________________________
0 no effect 5 56-65
1 10-25 6 66-75
2 26-35 7 76-85
3 36-45 8 86-99
4 46-55 9 100
-- not tested
______________________________________
TABLE IV
______________________________________
Insecticidal Evaluation Of N-arylthiohydrazone Compounds
% Mortality
SAW WCR TBW
Compound (1000 (300 (50 (10 (300 (100
(Ex. No.)
ppm) ppm) ppm) ppm) ppm) ppm)
______________________________________
1 9 9 9 9 1 0
2 -- 9 9 0 7 3
3 9 0 0 0 2 --
4 9 9 9 7 9 6
5 -- 0 -- -- 0 0
6 -- 8 9 0 2 0
7 -- 2 6 0 0 0
8 -- 9 9 2 6 2
9 -- 9 3 1 0 0
10 -- 6 0 -- 0 0
11 9 9 5 5 -- --
12 -- 9 9 0 9 0
13 -- 9 0 0 5 0
14 -- 9 8 1 8 0
15 -- 9 9 9 9 0
16 9 0 0 0 -- --
17 9 9 9 0 9 9
18 9 9 9 9 9 0
19 9 9 9 7 7 0
20 9 9 5 0 -- --
21 -- 0 0 0 3 0
25 7 -- 9 -- -- --
26 0 -- 9 2 -- --
27 9 5 4 -- 8 0
______________________________________
EXAMPLE 51
Insecticidal And Acaricidal Evaluation Of N-Arylthiohydrazone, S-Oxide
Compounds
Test solutions are prepared by dissolving the test compound in a 35%
acetone in water mixture to give a concentration of 10,000 ppm. Subsequent
dilutions are made with water as needed.
Tetranychus urticae(OP-resistant strain), 2-spotted spider mite (TSM)
Sieva limabean plants with primary leaves expanded to 7-8 cm are selected
and cut back to one plant per pot. A small piece is cut back to one plant
per pot. A small piece is cut from an infested leaf taken from the main
colony and placed on each leaf of the test plants. This is done about 2
hours before treatment to allow the mites to move over to the test plant
to lay eggs. The size of the cut, infested leaf is varied to obtain about
100 mites per leaf. At the time of test treatment, the piece of leaf used
to transfer the mites is removed and discarded. The newly mite-infested
plants are dipped in the test solution for 3 seconds with agitiation and
set in the hood to dry. After 2 days, one leaf is removed and mortality
counts are made. After 5 days, another leaf is removed and observations
are made of mortality of the eggs and/or newly emerged nymphs.
Empoasca abrupta, adults, western potato leafhopper (LH)
A sieva limabean leaf about 5 cm long is dipped in the test solution for 3
seconds with agitation and placed in a hood to dry. The leaf is placed in
a 100.times.10 mm petri dish containing a moist filter paper on the
bottom. About 10 adult leafhoppers are added to each dish and the
treatments are kept for 3 days before mortality counts are made.
Aphis fabae. mixed instar, bean aphid (BA)
Pots containing single nasturtium plants (Tropaeolum sp.) about 5 cm tall
are infested with about 100-200 aphids one day before the test. Each pot
is sprayed with the test formulation for 2 revolutions of a 4 rpm
turntable in a hood, using a #154 DeVilbiss atomizer. The spray tip is
held about 15 cm from the plant and the spray directed so as to give
complete coverage of the plants and the aphids. The sprayed pots are set
on their sides on white enamel trays and held for 2 days, following which
mortality estimates are made.
Employing the procedures described in Example 50 and above, the test
compounds are evaluated using the rating system described in Example 50.
The data obtained are reported in Table V below. When two or more tests
are conducted, the results are averaged.
TABLE V
__________________________________________________________________________
Insecticidal And Acaricidal Evaluation Of
N-Arylthiohydrazone, S-Oxide Compounds
% Mortality (ppm)
SAW WCR TSM LH TBW BA
Compound (Ex. No.)
1000
300
50
10
300
100
100
300
100
100
__________________________________________________________________________
28 9 9 9 9 8 8 9 9 9 0
29 9 9 9 9 9 9 9 9 9 9
30 9 9 9 9 8 4 9 9 9 0
31 9 9 9 9 8 9 9 9 9 0
32 9 9 9 5 0 -- -- -- -- --
33 9 9 9 5 8 8 5 9 9 8
__________________________________________________________________________
EXAMPLE 52
Insecticidal And Acaricidal Evaluation Of N-Arylthiohydrazone, S,S-Dioxide
Compounds
Following the procedures described in Examples 50 and 51, test compounds
are evaluated against a variety of insect and acarid species. The rating
system is the same as that described in Example 50. The data obtained are
reported in Table VI below. When two or more tests are conducted, the
results are averaged.
TABLE VI
__________________________________________________________________________
Insecticidal And Acaricidal Evaluation Of
N-Arylthiohydrazone, S,S-Dioxide Compounds
% Mortality (ppm)
SAW WCR TSM LH TBW BA
Compound (Ex. No.)
1000
300
50
10
300
100
100
300
100
100
__________________________________________________________________________
34 9 9 9 9 9 9 9 9 9 0
35 9 9 9 9 9 8 0 9 7 8
36 -- 9 9 9 9 9 9 9 7 8
37 9 9 9 8 9 8 6 9 8 0
38 9 -- 9 2 9 -- -- -- -- --
40 9 -- 9 0 9 9 9 0 0 0
41 9 9 9 8 9 7 9 6 0
42 9 9 9 9 9 9 0 6 0 0
43 -- 9 9 8 9 8 9 9 6 7
44 7 1 7 4 4 0 2 0 0 0
45 9 9 9 7 8 8 9 9 9 0
__________________________________________________________________________
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